CA1100975A - Azolyl ether derivatives and their use as fungicides - Google Patents

Abstract

Abstract of the Disclosure Azolyl ether derivatives of the formula

Description

~L1!D6~975 The present invention relates to certain new azolyl ether deriv-atives~ to a process for their preparation and to their use as fungicides.
It has already been disclosed that certain azole derivatives, in particular, 3,3-dimethyl-1-phenoxy-1-(1,2,4-triazol-1-yl)- or imidazol-l-yl-butan-2-ols and 3,3-dimethyl-1-(imidazol-1-yl)-1-phenoxy-butan-2-ones substi-tuted in the phenyl part, and ~-(imidazol-l-yl)-~-phenoxy-acetophenones sub-stituted in the phenoxy part have good fungicidal proper*ies (see DT=OS ~Ger-man Published Specification) 2,324,010, DT-OS (German Published Specification)

2,333,354 and DT-OS ~German Published Specification) 2,325,156). However, their activity is not always completely satisfactory, especially when low amounts and concentrations are used.
The present in~ention now provides, as new compounds, the azolyl ether derivatives of the general formula - O - CH - CH - Y ~I) n ~ N

in which A is CH or a nitrogen atom, R is alkyl; alkenyl; alkynyl; benzyl substituted with a substituent selected from halogen, cyano, nitro, alkyl, alkoxycarbonyl, and halogenoalkyl;
phenyl; or phenyl substituted by nitro, cyano or alkoxycarbonyl, and option-ally additionally substituted by a substituent selected from halogen, alkyland halogenoalkyl;
is halogen; alkyl; alkoxy; alkylthio; alkylsulphonyl; halogeno-; alkyl; alkoxycarbonyl; nitro; cyano; phenyl; phenoxy; phenylthio; or phenyl, phenoxy or phenylthio substituted by a substituent selected from halogen, cyano, nitro and halogenoalkyl;
n is 0, 1, 2, 3, 4 or 5;
Y is alkyl; alkyl substituted with a substituent selected fromhalogen, hydroxyl, cyano, and the grouping -CO-ORl; -Co-NR2R3 or -O-CO-R ;

~ ~ - 2 -97'S
phenyl; or phenyl substituted by halogen;
R is alkyl; ~:
R2 and R3 each independently is hydrogen; alkyl; phenyl or phenyl substituted by halogen; and R4 is alky].; halogenoalkyl; phenyl; ben~yl; phenyl or benzyl substi-tuted by hslogen; or cycloalkyl, or a non-phytotoxic salt or metal complex thereof.
The compounds of the present invention have been found to have powerful fungicidal properties.
Preferably, R represents alkyl, alkenyl or alkynyl with up to 4 carbon atoms in each case, or represents benzyl or monosubstituted or polysub-stituted benzyl~ the substituents being selected from halogen (especially fluorine, chlorine or bromine), cyano, nitro, alkyl with l to 4 carbon atoms, alkoxycarbonyl with l to 4 carbon atoms in the alkyl part and halogenoalkyl with up to 2 carbon atoms and up to three halogen atoms ~especially fluorine and chlorine, wi~h tri.fluoromethyl being mentioned as an example of such halogenoalkyl), or represents phenyl which is optionally substituted by nitro, cyano or alkoxycarbonyl with 1 to 4 carbon atoms in the alkyl part, an addi-tional substituent being optionally present, which is selected from halogen (especially fluorine, chlorine or bromine), alkyl with l to 4 carbon atoms and halogenoa].kyl with up to 2 carbon atoms and up to three halogen atoms (es-pecially fluorine and chlorine, with trifluoromethyl being mentioned as an example of such halogenoalkyl);
X represents halogen (especially fluorine, chlorine or bromine), nitro, cyano, Cl-C4 alkyl, Cl-C4 alkoxy, Cl-C4 alkylthio, Cl-C4-alkylsulphonyl, alkoxycarbonyl , : ~ - 3 -. . .-. ' ~;-, . . . . - :
. :~ : ::.: -. :: :. : : :;

with 1 to 4 carbon atom~ in the alkyl part, halogeno.~lkyl with up to 4 carbon atoms and up to 5 halogen atoms (especially with up to 2 carbon atoms and up to three identical or di.~ferent halogen a~oms, especially ~luorine and chlorine~ w:ith trifluoromethyl being mentioned as an example of ~uch halogenoalkyl)~ or optionally substituted phenyl, phenoxy or phenylthio, the substituents being selected from halogen (especially fluorine, chlorine and b~omine), c~ano, nitro and halogenoalkyl with up to 2 carbon atoms and up to 3 identical or different halogen atoms (especially ~luorine and chlorine, with trifluoro-methyl being mentioned as an example of such halogeno-alkylj;
n represent 0, 1, 2 or ~; and Y represents straight-chain or branched alkyl with 1 to 9 carbon atoms, which can optionally carry one or more substîtuents selected from halogen (especially chlorine or bromine), hydroxyl, cyano, the grouping : -C0-ORl wherein Rl repreSentS alkyl with 1 to 4 carbon atoms, the grouping -Co-NR2R3 wherein R2 and R3 are identical or dirferent and represent hydrogen, alkyl with 1 to 4 carbon atoms or phenyl which is optionally sub-stituted by halogen, or the grouping -o-Co-R4 wherein R4 represents alkyl with 1 to 18 carbon atoms, halogeno~
alkyl with 1 to 4 carbon atoms and 1 to 3 halogen atoms (especially fluorine or chlorine), phenyl or benzyl, optionally monosubstituted or polysubstituted by halogen (especially ~luorine or chlorine),or cycloalkyl with 5 or 6 carbon atomsS or Y represents.phenyl that is optionally monosubstituted or polysuhstituted by halogen (especially ' Le A 18 0~8 - 4 -' , ;, .. ,. : . . .

7~i fluorine, chlorine or bromine).
It is particularly preferred that Y represent tert.-butyl, 2,4-dichlorophenyl, 1,1-dimethyl-2-chioro(bromo)-ethyl or 2-ethoxy~methoxy)-carbonyl but-2-yl.
The compounds of the formula (I) possess two asymmetric carbon atoms; they can thus exist in the form of the two geometric isomers (erythro form and threo form), which can be obtained in varying proportions. In both cases, they exist in the form o~ optical isomers. The formula ~I) is intended to embrace all the isomers.
The present invention also provides a proces~ for the preparation o~ an azolyl ether derivative of the formula (I), in which an alcoholate of a l-azolyl-2-hydroxy-1-phenoxy-alkane derivative, of the~ formula OM

~ 15 X ~ N

: N -in which A~ X, Y and n have the meanings stated above and M represents an alkali ~etal or a quaternary ammonium or phosphonium group 9 is reacted with a halide of the general formula R - Hal ~III), in which R has the meaning stated above and Hal represents chlorine or bromine, in the presence of a diluent.
In the ~eneral formula (II) M preferably represents Le A 18 038 - 5 -7~

lithium, sodium3 potassium, tetrabutylammonium3 N-benzyl-N,N~N-trimethylammonium, hexadecyl-trimethylammonium, 2-hydroxyethyl-trimethyl-ammonium, tetraethyl-ammonium, tetramethyl-ammonium, tetra-n-propyl-ammonium, (cyclo-propylmethyl)-trimethyl-ammonium3 methyl-trioctylammonium, N-phenyl-N,N,N-trimethyl-ammonium, N-(4-methylbenzyl)-N,N,N-trimethylammonium3 N-benzyl-N~N-dimethyl-N-dodecyl-ammonium, N,N-dibenzyl-N,N-dimethyl-ammonium~ benzy~-dimethyl n-hexadecyl-ammonium, benzyldimethyl-tetradecyl-ammonium~ benzyl-tributyl-ammonium, benzyl-triethyl-ammonium, butyl-tripropyl-ammonium~ octadecyl-trimethyl-ammonium, tetrahexyl-ammonium, tetra-octyl-ammonium, tetra-pentyl-ammonium, tricaprylmethyl-ammonium, hexa-decyl-pyridini~m, tetraphenylphosphonium, hexadecyl-tributyl-phosphonium~ ethyl-triphenyl-phosphonium or methyl-triphenyl-phosphonium.
Furthermore, the azolyl ether derivatives of the formula (I) can be converted into salts by reaction with acids, and the corresponding metal complexes can be obtained by reaction with metal salts.
Surpri~ingly, the azolyl ether derivatives accordin~
to the present invention have a considerably hi~her fungicidal activity, especially against species o~ powdery mildew, than the l-azolyl-3,3-dimethyl-1-phenoxy-butan-2-ones and -ols and ~-(imidazol-l-yl)-~-phenoxy-acetophenones, which are knoun from the state o~ the art and are the most closely related substances chemically and from the point o~
view o~ their action. The active compounds according to the invention thus represent an enrichment o~ the art.
I~ the sodiwn alCholate of 1-(4-chlorophenoxy)-1-Le A 18 038 - 6 -- (1,2~4-triazol-1-yl~-butan-2-ol and allyl chloride are used as starting materials, the course of the reaction can be represented by the following equation:

ONa ~Cl-CH2-CH-CH2 Cl- ~ -O-CH-CH-C(CH3)3 ~aCI

N- l I
~-CH
Cl- ~ -O-CH-CH~C(CH~ )3 ~1~

The alcoholates of the formula (II) have ~ot hitherto been disclosed in the literature. They are obtained by reacting the corresponding 1-azolyl-2-hydroxy-l~phenoxy~
alkane derivatives with suitable strong bases~ such as alkali metal amîdes or hydride~ or quaternary ammonium : 10 hydroxides or phosphonium hydroxides, in an inert solvent.
Some of the l-azolyl-2-hydroxy-1-phenoxy-alkane derivatives ,~
are known (see DT-OS (German Published Speci~ication) ~ 2,324,010 and DT-OS (German Publi~hed Specification) ;~ 2,333~354) and ~ome are the ~ubjeGt of our German Patent : 15 Applications P26 32 603 of 20.7.1976, P 26 32 602 of 20,7,1976, P 26 35 663 of 7,8.1976, P 26 35 666 of 7,8. 1976~
P 27 05 677 of 11.2.1977 and P 27 05 678 of 11.2.1977. They are obtained by reducing the corresponding azolyl-alkanone derivatives of the general ~ormula ~ - O - CH - CO - Y
Xn ~ A (IV)~
N

~- Le A 18 o38 - 7 -- ~ : . , :: . , :
,, , ~ . . . . .

in which A, X, Y and n haYe the meanings stated above, in a manner which i~ generally-known, by meanæ of complex hydrides, such as sQdium borohydride, by means of aluminiu~
isopropylate or by using formamidine-sulphinic acid and alkali metal hydroxide (see also the preparative Examples given later in this text).
Some o~ the compounds o~ the~rormula (IV) are al~o known tsee DT-OS tGerman Published Specification) 2,201~063 and DT-OS (German Published Specification) 2~3259156)~
and some o~ them are the subject of the above~m~ntioned German Patent Applica~ions. They are obtained by reacting halogenoketones of the general formula - O - CH - CO - Y (V), ~ Hal in which X~ Y~ and n have the meaning~ stated above and Hal represents chlorine or bromine, with known azoles o~ the general ~ormula HN/ ~ (VI), in which ; A has the meaning stated above~
în the presence of a diluent and an acid-bindin~ agent (see al~o the prep~tion Examples).
The halogenoketones of the formula (V) are known from the above-mentioned German Offenlegung~schriften (German : Le A 18 038 - 8 -9'75 Pu ~ished Specifications) or are the subject of the above-mentioned German Patent Applications~ They can be pre-pared, for example, by reacting known phenols o~ the general formula ~ OH (VII), Xn in which X and n have the meaning~ stated above, with known halogenoketones of the general ~ormula Hal-CH2-CO-Y (VIII)~
in which Y has the meaning stated above and Hal represents chlorine or bromine.
The ac~ive hydrogen atom which still remains is then : replaced by halogen in the customary manner (see also the preparative Examples).
Examples of the l-azolyl-2-hydroxy-1-phenoxy-alkane derivatives ~rom which the alcoholates of the formula (II) are derived are (azolyl representing either the 1~2,4-triazol-l-yl radical or the imidazol-l-yl radical):
1-azolyl-1-phenoxy~2 hydroxy-3,3-dimethyl-butane, 1-azolyl~
1-(4-chlorophenoxy)-2-hydroxy-3,3-dimethyl-butane~ l-azolyl-1-(2,4~dichlorophenoxy)-2-hydroxy-3,3-dimethyl-butane, 1-azolyl-1-~4-bromophenoxy)-2-hydroxy-3,3-dlmethyl-butane, ; l-azolyl-1-(4-biphenylyloxy)-2-hydroxy-3,3~dimethyl-butane, 1-azolyl-1-(4'-chloro-4-biphenylyloxy)-2-hydroxy-3,3-dimethyl butane, l-azolyl-1-(4-phenoxyphenoxy)-2-hydroxy-

3,3-dimethyl-butane a 1-azo~yl-1-(4-phenylthiophenoxy)-Le A 18 o38 - 9 -.. . . . . . . . .. ..

`

1~ 97S

2-hydroxy-3,3-dimethyl-butane, 1.-azolyl-1-(4'-chloro-4-phenoxyphenoxy)-2-hydroxy-3,3-dimethyl-butane, l-aæolyl-l-(4'-chloro-4-phenylthiophenoxy)-2-hydroxy-3~3-dimethyl-butane~ l-azolyl-1-~4-nitrophenoxy)-2-hydroxy~3,3-dimethyl-butane, 1-azolyl-1-(4-methoxycarbonylphenoxy)-2-hydroxy-3,3- dimethyl-butane ~ l-azoly 1-1- ( 4-fluorophenoxy)-2-hydroxy-3,3-dimethyl-butane3 1-azolyl-1-(4-chlorophenoxy) 2-hydroxy-~,3-dimethyl-4-chloro-butane, 1-azolyl-1-(2,4-dichlorophenoxy)-2-hydroxy~3,3-dimethyl-4-chloro-butane, 1-azolyl-1-(4-bipheny~yloxy)-2-hydroxy-3,3-dimethyl-4-chloro-butane~ l-azolyl-1-(4'-chloro~4-biphenylyloxy)-2-hydroxy-393-dimethyl-4-chloro-butane, 1-azolyl-1-(4' chloro-4-ph~noxyphenoxy)-2-hydroxy-3,3-dimethyl-4 chloro-bu~ane, l-azolyl-l-(4-nitrophenoxy)-2-hydroxy-3,3-dimethyl-

4-chloro-butane, 1-azolyl-1-(4-chlorophenoxy)-2-hydroxy-3-methyl-4-acetyl-butane, 1-azolyl-1-(2,4-dichlorophenoxy)-2-hydroxy-3-methyl-4 acetyl-butane, 1-azolyl-1-(4-biphenyl-yloxy)-2-hgdroxy-3-methyl-4-acetyl-butane, l-azolyl-l-(4'-chloro-4-biphenylyloxy)-2-hydroxy-3-methyl-4-acetyl-butane~ 1-azolyl-1-(4'-chloro-4-phenoxyphenoxy)-2 hydroxy-3-methyl-4-acetyl-butane, 1-aæolyl-1-(4-nitrophenoxy)-2-hydroxy-3-methyl-4-acetyl-butane, 1-azolyl-1-(4-chloro-phenoxy3-2-hydroxy-3-methyl-3-ethoxycarbonyl-butane, l-azolyl-l-(2 3 4-dichlorophenoxy)-2-hydroxy-3-methyl 3-ethoxy-carbonyl-butane, 1-azolyl-1-(4-biphenylyloxy)-2-hydroxy-3-methyl-3-ethoxycarbonyl-butane, l-azolyl-l-(4'-chloro-4~biphenylyloxy)-2-hydroxy-~-methyl-3-ethoxy-carbonyl-butane, l-azolyl-1-(4'-chloro-4-phenoxyphenoxy)-2~hydroxy-3-methyl-3-ethoxycarbonyl-butane, l-azolyl~l-~4-nitrophenoxy)-2-hydroxy 3-methyl-3-ethoxycarbonyl-Le A 18 038 - 10 -butane, l-azolyl-1-(4-chlorophenoxy)-2-hydroxy-3-ethoxy carbonyl-3-methyl-pentane, l-azolyl-1-(234-dichloro-phenoxy)-2-hydroxy-3-ethoxycarbonyl-3-methyl-pentane, l-a~olyl-l-(4-biphenylyloxy)-2-hydroxy-3-ethoxycarbonyl-3-methyl-pentane, 1-azolyl-1-(4'-chloro-4-biphenylyloxy)-2-hydroxy-3-ethoxycarbonyl-3-methyl-pentane, l-azolyl-l-~4'-chloro-4-phenoxyphenoxy)-2-hydroxy-3-ethoxycarbonyl-3-methyl-pentane, 1-azolyl~l-(4-nitrophenoxy3-2-hydroxy-3-ethoxycarbonyl-3-methyl-pentane~ 1-azolyl~ 4-chloro-phenoxy)-2-hydroxy~3 butyl-3-methoxycarbonyl-heptane~
l-azolyl-1-(2,4-dichlorophenoxy)-2-hydroxy-3-butyl~3-methoxycarbonyl-heptane, l-azolyl-1-(4-biphenylyloxy)-2-hydroxy-3-butyl-3-methoxycarbonyl-heptane, l-azolyl-l-(4'-chloro-4-biphenylyloxy)-2-hydroxy-3-butyl~3-methoxy~
carbonyl-heptane, 1-azolyl-1-(4'-chloro-4-phenoxyphenoxy)-2-hydroxy-3-butyl-3-methoxycarbonyl-heptane, l-azolyl-1-(4-nitrophenoxy)-2-hydroxy-3-butyl-3-methoxycarbonyl hepkane, l-azolyl-1~(4-chlorophenoxy)-2~hydroxy-2-(2,4-dichlorophenyl)-ethane, l-azolyl-1-(2,4-dichlorophenoxy)-2-hydraxy-2-(2,4-dichlorophenyl)-ethane~ 1-azolyl-1-(4-biphenylyloxy)-2-hydroxy-2-(2,4-dichlorophenyl)-ethane, l-a~olyl-1-(4'-chloro-4-biphenylyloxy)-2-hydroxy-2-(~,4-dichlorophenyl)-ethane, l-azolyl~1-(4'-chloro-4-phenoxy-phenoxy)-2-hydroxy-2-(2,4-dichlorophenyl)-ethane and 1-azolyl-1-(4-nitrophenoxy)-2~hydroxy-2-(2,4~dichloro-pheny].)-ethane.
The starting materials o~ the formula ~III) are generally known compounds of organic chemistry. Examples which may be mentioned are: methylene chloride, ethylene chloride~ n-propyl bromide, n-butyl bromide, t-butyl Le A 18 0~8 9t~5 bromide~ allyl bromide, allyl chloride, vinyl bromide, buten-2-yl chloride, propynyl chloride, p-cyano-o-nitro-chlorobenzene, p-nitrochlorobenzene, p-nitrobromobenzene, benzyl chloride, p-chlorobenzyl chloride, 2,4-dichloro-benzyl bromide, 4-nitrobenzyl chloride and 4-cyanobenzyl chloride .
Prererred salts of the compounds o~ the ~ormula (I) are, for reasons of toxicity~ physiologically acceptable salts, these generally being salts with physiologically acceptable acids~ The preferred acids are the hydrogen halide acids (for example hydrobromic acid and especially hydrochloric acid), phosphoric acid, nitric acid, sul-phuric acid, monofunctional and bifunctional carboxylic acids and hydroxycarboxylic acids (for example acetic acid3 maleic acid, succinic acid, fumaric acid, tar~aric ~cid~ citric acid, salicylic acid, sorbic acid and lactic acid) and sulphonic acids (~or example ~-toluenesulphonic acid and lD5-naphthalenedisulphonic acid).
The salts o~ the compounds of the formula (I) can be obtained in a simple manner by customary salt ~ormation methods, for example by di~solving the base in ether, ~or example diethyl ether, and adding the acid, for example nitric acid, and can be isolated in a known manner, for example by filtration, and optionally purified.
The preferred metal complexes of the compounds o~ the rormula (I) are physioaogically acceptable. Preferred salts for the preparation o~ such complexes are those o~ metals o~
main g~oups II to IV and of sub-groups I and II and IV to VIII, for example copper, zinc~ manganese, magnesium, tin3 3Q iron and nic~el. Possible anions o~ the salts are those ;~

Le A 18 038 - 12 which are derived from phy3iologically acceptable acid~, prererably the hydrogen halide acids (for example hydro-chloric acid), phosphoric acid~ nitric acid and sulphuric acid.
The metal complexes of the compound3 of ~he formula (I) can be obtained in a simple manner by customary processe~, for example by dis~olving the metal salt in alcohol 9 for example ethanol, and adding the ~olution to the compound o~ the formula (I). The metal salt complexes can be isolated in a known manner, ~or example by ~
tration, and optionally purified by recrystallisation.
Preferred diluents which can be used for the re-action between the compound (II) and (III) are lnert organic solvents, especially ethers, such as diethyl ether and dioxan; benzene; in individual case~ also chlorinated hydrocarbons J such as chloroform, methylene chloride or carbon tetrachloride; and hexamethylphosphoric acid triamide~
The reaction temperature3 can be varied within a relatively wide ran~e. In general~ the reactlon is carried out a~ ~rom 20to 150C, preferably at the hoiling point o~
the solvent, for example at ~rom 60 to 100C.
In carrying out the process according to the in-vention9 1 to 2 moles o~ the halide of the formula (IIl) are pre~erably used per mole o~ the alcoholate o~ the fo~mula (II). In order to i~olate the end products~ the reaction mixture is freed ~rom sol~ent, and water and an organic solvent are added to the residue. The organic phase is separated off, worked up in the customary manner and purifiedg and the salt is optionally prepared.

Le A 18 038 ~ 13 -In a pre~erred embodiment, the procedure i8 to use a l-azolyl-2-hydroxy-1 phenoxy-alkane derivative as the starting materlal, to convert this derivative into the alkali metal alcoholate of the formula (II) in a suitable inert organic solvent by means of an alkali metal hydride or alkali metal amide9 and to reac~ the alcoholate Wit~l a halide of the formula (III) immediately, wi~hout i80-lation, the compounds o~ the formula (I) according to the invention being obtained in one operation, with alkali metal halide being elimi~ated.
According to a ~urther preferred em~odîment, the preparation of the alcoholates of the formula (II) and the reaction according to the invention are carried out in a two-pha~e system~ such as, ~or example, aqueous sodium hydroxide solution or potassium hydroxide solution/toluene or methylene chloride, with the addition of 0.01-1 mol o~ a phase ~rans~er catalyst~ such as, for example, ammonium or phoæphonium compounds, the alcoholate~ forming in the organic phase or at the interface and being reacted with the halides present in the organic phase.
Examples of particularly active compounds a~ccording to the invention are the following: 1 (4-chlorophenoxy)-2-(294-dinitrophenoxy)-3,3-dimethyl-l-(1,2l4-triazol-l-yl)-bu~ane~ 2-propargyloxy-~(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butalle, 2-propargyloxy-1~(4-chloro-phenoxy3-~,3-dimethyl-1-imidazol-1-yl~butane~ 2-methoxy-1-(4-cyanophenoxy)-393-dimethyl-1-~1,234-triazol-l yl)-butane~
2-methoxy-1-(4-methoxy~carbonylphenoxy)-3,3-dimethyl~l-~192,4-triazol-l-yl)-butane, 2-methoxy-1-(3-trifluoro-methylphenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butane, Le A 18 038 14 7~

2~ethoxy-1-(4-nitrophenoxy)~3~3-dimethyl~ 2,4-triazol-l-yl)-pentane, 2-methoxy~ 2,4-dichlorophenoxy)-3,3-dimethyl-l-imidazol-l-yl-butane~ 2-ethoxy~ 4-chloro-2-methyl-phenoxy)-3,3-dimethyl~ 2~4-triaæol-1-yl)-butane, 2-ethoxy-1-(4-chlorophenoxy)-3-methyl-3-ethoxy-carbonyl-l-(1,2,4-~riazol l-yl)-pentane~ ~ allyloxy-l-t4~chlorophenoxy)-3-methyl-3-ethoxycarbonyl-1-imidazol 1 yl-pentane, 2-met~oxy-1-(4-chlorophenoxy)-3-butyl-3-methoxycarbonyl-l-imidazol-l-yl-heptane, 2-(2S4-dichloro~
benzyloxy) 1-(4-chlorophenoxy)~3-methyl-3-methoxycarbGnyl~
2~4-tria~ol-1-yl)-hexane, 2-(4-chlorobenzyloxy)-1-(4-chlorophenoxy)-3-ben%yl-3-methoxycarbonyl-1-(1,2,4-triazol-l-yl)-heptane, 2-methoxy-1-(4-chlorophenoxy)-3-~e~hyl-3-chloromethylene-1-(1,2,4-triazol-1-yl)-butane~
2-ethoxy-1-(4-chloropheno~y)-3-methyl-3-chloromethylene-1-imidazol-l-yl-butane, 2-ethoxy-1-(4-chlorophenoxy)-3-methyl-3-bromomethylene-1-(1,2,4-triazol-l~yl)-butane~
2;alkoxy-1~(4-chlorophenoxy)-3~3-di-chloromethylene-1-(1~2,4 triazol-1-yl)-butane, 2-ethoxy-1-(4-chlorophenoxy~-3,3-dimethyl-4-acetoxy-1-(1,2,4-triazol-1-yl)-butane and 2-allyloxy-1-(4-chlorophenoxy)-3,3-dimethyl-4-h~droxy-1-(1,2,4-triazol-1-yl)-butane.
Further active compounds ar0 mentioned in the preparative Examples given later in this text.
The active compounds according to the invention exhibit a powerful fungitoxic action~ and a bacterio-toxic action.~hey do not damage crop plants in the con-cen~rations re~uired for combating fungi and bacteria.
For these reasons, they are suitable ~or use as plant protection agents ~or combating fungi and bacteria.

Le A 18 0~8 ~ 15 -~, ~ ~ - . . . ' !

Fungitoxic agents are employed in plant protection for combating ~ ~ ~ e~es~ O mycetes J' '~
an~
The active compounds according to the invention have a broad spectrum of aGtion and can be used against parasitic fungi which attack above-ground parts o~ plants or which a~tack ~he plants through the soil9 as ~ell as against seed borne pathogens.
They display a particularly good activity against 10 parasitic fungi on above-ground parts of plants, such as s~ecies of ~ ~ 3pecies of ~ and species of Venturia, and also against species o~ ~
and species of Pellicularia. Good actions are achieved against the pathogens of apple scab (Fusicladium 15 dendritioum)9 of powdery mildew of apples (~
leucotricha), of powdery mildew of cucumbers ( ____ ciohoraoearum) and against the fungi ~ oryzae and Pellicularia sasakii. Furthermore~ they exhibit . ~
a high activity against cereal diseases, such as against 20 powdery mildew of cereals, cereal rust and powdery mildew of barley.
A ~act to be singled out is that the active compounds according to the invention not only display a protective action but are also systemically actiYe. Thus it proves 25 possible to protect plants against ~ungal attack by ...
supplying the active compound ko the ~bove-ground parts of the plantt~ugh the soil and the root or through the seed.
As plant protection agents, the compounds according to the invention can be used for the treatment of 80ilg ~0 for the treatment of seed and for the treatment of above-Le A 18 038 16 -ground parts of pl~lts.
The active compounds can be converted into the customary formulations D uch a~ solutions, emulsions, wettable powders 3 3u~pension~, powders 9 dusting agents a foams, pastes, soluble powders~ granules; aerosol~, suspension-emulsion concentra~es, ~eed-treatment powder~
natural and synthetic material~ impregnated with active compound9 Yery fine cap~ule~ in polymeric sub~tances, ooating compositions for u~e on ~eedg and ~ormulations u~d with burning equipment~ such as fumigating cartridges, fumigating cans and ~umiga~ing coils~ a~ well as ULV
cold mist and warm mi~ ~ormulations.
These formulation~ may be produced in known manner, for example by mixing the active compounds with extenders, that i8 to say liquid or lique~ied ~aseous or solid diluents or carriers~ optionally with the use of surface-active agents, ~hat is to say emulsifying agents and/or di~persing agen~s and~or foam-formin~ agents. In the case of the use Or water as an extender, organic solvents can~ for example, also be used as auxiliary solvents.
~s liquid solvents diluents or aarrier~ 3 especially so1vents~ there are suitable in the main, aromatic hydrocarbons, such a~ xylene, toluene or alkyl naph-thalene$, chlorinated aromatic or chlorinated aliphatic hydrocarbons ~ such aa chlorobenzene~, chloroethylenes or methylene chloride~ aliphatic or alicyclic hydro-carbons~ such a~ cyclohexane or paraffins, for example mineral oil fractio~s, alcohol~, such as butanol or glycol as well as their ethers and e~ters, ~etones 9 ~uch as acetone, methyl ethyl ketone, methyl i~obutyl Le A l8 038 - 17 -g7~

ketone or cyclohexanone3 or strongly polar ~olvents9 su~h as dimethylf~o~namide and dimethylsulphoxide, as well as water.
By lique~ied gaseous diluentæ or carriers are meant liquids which would be gaseou~ at normal temperature and under normal pressure ~ for example aerosol propellant~ a such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
As solîd carriers there may be used ground natural minerals~ such a~ kaolins, clays, talc9 chalk, quart~., at~apulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid~ alu~ina and silicates. As solid carriers ~or granules there may be used crushed and fractionated natural rock~ such as calcite, marble, pumice 9 sepiolite and do}omite, as well a~ synthetic granules of inorganic and organic meals~ and ~ranule~ of organic material such a~ sawdust, coconut shells, maize cobs and ~obacco stalks.
As emulsifying and/or foam-forming agents there may be uæed non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fat~y alcohol ethers~ ~or example alkylaryl polyglycol ethersa alkyl su~phonates, alkyl ~ulphates9 aryl sul-phonates as well as albumin hydrolysis products. Di3-persing agents include~ for example, lignin sulphite waste liquor~ and methylcellulose~
The active compounds according to the invention can be present in the ~ormulations as a mixture with other active compounds, such as Yungicides~ insecticides~
acaricides~ ne~aticides~ herbicides 9 bird repellants, Le A 18 o38 - 18 -.. . .

'75 growth factors, plant nutrients and agents for improving soil ~tructure.
The formulations in general con~ain ~rom 0.1 to 95 per cent by weigh~ o~ active compound~ preferably ~rom 0.5 to 90 per cent.
The active compound3 can be used a~ such, as their ~ormu~ation3 or as the use ~orms prepared there~rom by ~urther dilution, such as ready-to-use solutionsj emulsion~, suspension~ powders 9 paste~ and granules.
~hey may be used in the customary manner" ~or example by wat~ring, spraying, atomi~ing, dusting, scattering9 dry dressin~, moist dres~ing9 wet dre~sing, slurry dres~in~
or encru~ting.
Especially when u~ed as leaf ~ungicides~ the active compound concentrations in the use forms can be varied within a ~airly wide range. They are~ in gene~al, ~rom Q.l to 0.00001 per cent by weight, preferably from 0.05 to 0.0001 per cent.
In the treatment of seed, amounts of active compound of 0.001 to 50 g, pre~erably 0.01 to 10 g, are generally employed per ki}~gram o~ ~eed~
For the treatment of soil, amounts oP active com-pound o~ 1 to 1,000 g,e~pecially 10 to 200 gt are generally employed per cubic metre o~ soil.
The present invention also provides a Pungicidal composition containing as active ingredient a compound oP the present inYention in admixture with a solid or lique~ied gaseou~ diluent or carrier or in admixture with a liquid diluent or carrier containing a surPace-active ~gent.

Le A 18 038 - 19 . .

-The pre~ent invention also pro~i~e~ a method of combating fun~;i which comprises applying to the ~ungi, or to a habitat thereor~ a compound of the pre~ent in-vent;on alone or in the ~orm o~ a compo~ition containi~g a~ active ingredient a compound o~ the present invention in admixture with a diluent or carrier.
The pre~ent invention further provide~ crops ~rotected from d~mage by fungilby being grown in area~ in which immediately prior to and/or during the time of the growing a compound o~ the present invention wa~ applied alone or in admixture with a diluent or carrier.
It will be seen that the usual methods of providing a harYested crop may be improved by the Present invention.
The ~ungicidal activity Or the compounds of thi~
invention is illustrated by the ~ollowing biotest Example~.
In these Examples, the compounds according to the present invention are each identifîed by the number (given in brackets) of the corre~ponding preparative Example, which will be found later in thi~ speci~ication.
2 0 The known compari~on compound~ are identified as rOllOw~:
o~
(A) - O N-~-O-CH-CH-C(CH3 )3 ~N~N

N Ll OH
(C~3 ) C-~ -O-lCH-CH-C(CH~ )3 (B) =
N

Le A 18 o38 - 20 -Cl-~ -O-CH-CO~C ( C~t )3 (C) ~

O-CH-CO~rC(CH3 )~
( D ~

~H
(E) _ Cl~ O-~H~CH-C(CH3 )3 ?N

(F) ~ Cl~ (CH,~
N

tG) ~) CH
~-O-CH-CH-C(CH3 )3 OH
CH3 OCO~ O-CH-CH-CtCH~
: (H ) = ~N~N
N _ll OH
(J) _ Cl-~-O-CH-CH-CH3 ~N`N

l)H
R~-O-CH-C~
( K ~ - ~

N x HCl Le A 18 038 - 21 -(L ) - Cl- ~-O-CH- CO~) Cl~

I:)H
o-CH-CH-C ( CH3 ~3 (M ) _ ~N`N
N_11 Cl OH
O-CH-CH-C(CH3 )~

N ~

Br-~-O-~H-CH-C ( CH

( P ) = ~1 N

,Cl OH
~-O-CH-CH-C(CH~

,Cl ( R ) - ~ -O-CH-CO~

x H~O x HCl te3t tapple)/protective Solvent: 4. 7 part~ by weight of acetone Emul~ifier: O. 3 part by weight of alkylaryl polyglycol ether Water: 95 p~rl;~ by weight The amount of active compound required ~or the d~ired concentration of the activ~ campound in the I.e A 18 038 - 22 ~

i~ . . . . .

S

apray liquid was mixed with the stated amount of sol~Yent~
and the concentrate was diluted with the stated amount`
of water which cQntained the ~tated amount of emul~i~ierO
Young apple seedlings in the 4 - 6 leaf stage were sprayed with the spray liquid until dripping wet.
The plant~ remained in a greenhouse for 24 hour~ at 20 deg.C and at a relative atmo~pheric humidity of 70%.
rrhey were then inocula'ced by dustin~s the Gonidia o~
the apple powdery mildew causative organi~m leuco~ir1cha) and placed in a greenhouse at a temperature of 21 - 2~ de~. C and at a relative atmo~pheric humidity o~ about 70%.
10 days after the inoculation9 the inrection of the seedling~ was determined. The asse~sment data were converted to ~ infection. 0% meant no infection; 100%
meant tha~ the plants were completely infected.
The active compounds, the concentrations of the : active compound~ and the re ults can be seen from the ~ollowing table:
~ a b 1 e test (apple)/protective Active In~ection in % at an active com-compQund pound concentration of ~1~_ (A) 100 - -(B) 100 - _ (C~ - 100 (D) _ 100

(5) - - 2~
(~2) - - 0 (1) -- -- O
(9) ~ _ O

Le A 18 038 - 23 -T a ~ 1 e ~ (continued) test (apple ) /protective Ac~ive In~ection in % at an active com-compourld pound conc~ntration o~

(10) - - O
(11~ - - 7 (12) - - 4 ( 13) - - 1 (14) _ _ 2 ~ 1 5 ) ~ 2 lû ( 16 ) - - 4 (1~) ~ ~ 55 (3) ~ ~ 7

(6) -- -- o t34) - 50 ~36) _ 30 (~7) ~ 57 ( 38 ) - 57 ~usioladium te~t (aPple)/protective Solven~: 4 . 7 parts by weight of acetone Emul~î~ier: 0. 3 part by weight oP alkylaryl polyglycol ether Water: 95 ~arts by weight The amount oP active compound required for the desired ooncentration o~ the active compound in the $pray liquid was mixed with the stated amount o~ ~olvent, ~nd the concentrate was diluted with the stated amount o~ water which contained the stated arnount o~ emul~ifier.
Y~ g appl~ ~eedlings in the 4 - 6 leaf stage were Le A 18 038 - 24 -.

sprayed with the ~pray liquid until dripping wet. The plant~ r~mained in a greenhouse ror 24 hours at 20 ~egrees C and at a relative atmospheric humidity of 70%, They were then inoculated with an aqueous conidium su~pen~ion of the appl~ ~cab causative organi~m (Fu~icl~dium dendritioum) and incubated ~or 18 hour~ in a humidity chamber at 18-20 de~ree~ ~ and at a relative atmosph~ric humidity of 100%.
The plants were then brought into a greenhouse agaln ~or 14 days.
15 days after inoculation, the infection Or the seedlinK~ wa~ determined. The as~essment data were converted to percent infection. 0% meant no infection;
lOOg meant that the plants were totally infected.
The active compounds~ the concentrations of the active compoun~s and the results can be seen ~rom the ~ollouing table:
T a b 1 e B
Fusicladium ~es~ (apple)/protective Active Infection in % at an acti~e com-~E) 83 (34~ 54 (36) 40 (37) 51 ~38) 40 (~0) 67 (42) 65 Exa~ple C
Shoot treatment test/powdery mildew o~ cereals ~leaf-destructive mycosi~)/protective -Le A 18 038 - 25 -... .

To produce a suitable preparation Or active comp~und, 0,25 part by weight of active compound was taken up in 25 parts by wei~ht of dimethyl~ormamide and 0.05 part by weight o~ alkylaryl polyglycol ether; 975 parts by weight o~ water were then added. The concentrate was diluted with water to the desired ~inal concentration o~ the spray liquor~
To test for protective activity, single-leaved young barley plants of the Amsel variety were sprayed with the preparation o~ active compound until dew-moistr After drying, the barley plants were dusted with spores o~ var. hordei.
After 6 days' dwell time o~ the plants at a tempera-ture of 21-22 ~eg.C and 80-90% atmospheric humidity the occurrence of mildew pustules on the plants wa~
evaluated, The degree Or infection was expressed as a per~entage of the infection of the untreated control p}ants. 0% deno~ed no in~ection and 100% denoted the same degree of in~ection as in the case of the untreated control. The active compound wa5 the more active, the lower wae the degree of mildew infection.
The active compounds, active compound aoncentrations in the spray liquor ~nd degrees of in~ection can be ~een from the table which ~ollows:
T a b 1 e C
Shoot treatment test/powdery mildew of cereals/protectiYe Active Active compound con- I~fection in %
compo~nd~ centration in the o~ the untreated spray liquor in % by control ._ ~
untreated - 100 Le A 18 038 26 -

7 S

T a_b l e C ~continued) Shoot treatment test/powdery mi1 dew of cereals /protective Active Ac~ive compound con~ Infection in %
compounds centration in the of the un-spray liquor in % by treated con-(F) ~ 0,01 26.3 (G) 0.01 21.3 (H) 0.01 37.5 (J) 0.01 78.8 (X) 0.01 66.3 (L) 0.01 46.3 (35) 0.0025 25.0 (36) 0.0025 ~ 0.0 (37) 0.0025 0.0 ~38) 0.0025 .
(39) 0.0025 36.3 (40)~ 0.0025 o.o (33) 0.0025 12.5 (32) 0.0025 0.0 (1) 0.0025 0.0 t9) 0.0025 O.o ~10) 0.0025 0.0 (30) 0.0025 0.0 (11) 0.0025 0.0 (12) 0.0025 0.0 2$ (13) O.OOZ5 0.0 ~14) 0.0025 o,o (15) 0.0025 0.0 (16) 0.0025 0.0 (18) 0.0025 0.0 ~e A 18 038 - 27 -.. . ... . . . . .. .. .

7~i , .. . .. . . . .. .. . .
Powdery mildew o~ barley 't' ~ ' ~ var.~ hor~el) ~fungal di~ease o~ cereal shoot~)/systemic The active compound wa~ u~ed aa a pulverulent seed treatment agent. ~hifi was prepared by extendin~ the particular active compound with a mixture of equal part~
by weight of ~alc and kieseIguhr to give a ~inely pulverulent mixture o~ the desired concentration o~ active compound.
For the treatment of seed~ barley seed was shaken L0 with the ex~ended active compound in a closed gla~ bottle.
The seed was sown at the rate of 3 x 12 grains in ~lowerpotsg 2 cm deep in a mixture of one part by volume of Fruhstorfer s~andard soil and one part by volume o~ quartz ~and.
The ~ermination and emergence took place under favourable conditions in a greenhouse. 7 days after ~owing, when the barley plants had developed their first leaf~ they were dusted with ~resh æpores of ~ ~ v~.
and grown on at 21-22 deg.C and 80-90% relative atmo3pheric humidity and 16 hour~' exposure to light.
Th~ typical mildew pu~tules ~ormed on the leaves over `
the cour~e of 6 days.
The degree of in~ection wa~ expressed as a percentage o~ the infection of the untreated control plant~. Thuæ, 0% denot~ no infection and 100% denoted the same degree of infection a~ in the ca~e o~ the untreated control.
The active compound wa3 the more active, the lower was the degree of mildew in~ection.
The ~ctive compounds and concentrations of active compound in the ~eed treatment agent, aæ well a~ the amount used of the latter, and the percentage infection Le A 18 038 - 28 -with mildew can be seen from the ~able wh;.ch follows~
' ~ a b 1 e D
Powdery mildew o~ barley test (~
var. h'ordei) /systemic Active Active com- Amount of Infection compounds pound con- dressing in % of centration used in 'che un-in the g/kg o~ treated dressing seed control in % by . ._ ~
no dressing - - lO0 (M) 25 lO lO0 (B) 25 lO 100 (~) 25 10 lO0 (5) 25 lO 10.0 ~32) ~5 lO 0.0 (l) 25 10 0.0 (9) 25 lO 0.0 (7) 25 lO 55.0 (33) 25 lO ~3-8 Pellicularia test ___ S~lvent: 11.75 parts by weight of acetone Dispersing agent: 0.75 part by weight of alkylaryl poly~lyc~l ether Water: g87.50 parts by weight The amount of active compound re~uired for the desired concentration of active compound in the spray liquor was mixed with the stated amount of the solvent 2S and of the dispersing agent and the concentrate was diluted with the stated amount of water.
Rice plants abou~ 2-4 ~eeks old were sprayed with the spray liquor until dripping wet. The plant~

Le A 18 038 - 2g -9~75 remained in a greenhouse at temperatures o~ 22 to 24 de~.C and a relative atmospheric humidity of about 70%
until they were dry. The plants were infected with a culture of Pellicula~i~ s~sakii grown on malt agar and __ __ were set up at 28 to 30 deg.C and lOOg relative atmosph0ric humidity. ;~
The in~ection at the leaf sheaths after 5 to 8 days was determined, in relation to the untreated but infected control. The e~aluation was made on a æcale from 1 to 9. 1 denoted 100~ action, 3 denoted good action, 5 denoted moderate action and 9 denoted no action.
The active compounds, the concentrations of the ac~ive compounds and the results can be seen fram the table which follows.
T a b 1 e E
Pellicularia test Active Infection at an acti~e compound (P) 9 (36) 3 (37) (38) 5 ~ ' Mycelium growth test Nutrient medium uæed:
20 parts by weight o~ agar-agar 200 parts by weight of potato decoction 5 parts by wei~ht o~ malt 15 parts by weight of dextrose 5 parts by weight of pept one ~0 2 parts by weight of disodium hydrogen phosphate - Le A 18 038 - 30 -0.3 part by weight of calcium nitrate Ra~io Or ~olvent mixture to nutrient medium:
2 parts by weight of solvent mixture 100 part~ by weighk of agar nutrient medium Composition of the solvent mixture:
0.19 part by wei~h~ o~ acetone or DMF
0.01 part by weight of emul~i~ier ~alkylaryl polyglyo~l ether) 1~80 parts by weight of water The amount of active compound r~quired ~or the desir~d active compound concentration in the nutrient medium was mixed with the stated amount o~ solvent mixture.
The concentrate was thoroughly mixed, in the stated proportion, with the liquid nutrient medium (which lS had been cooled to 42 deg.C) and was then poured into ~: Petri dishes of 9 cm diameter. Control plates to which t~e preparation had not been added were also set up.
When the nutrient medium had cooled and solidified, the plates were inoculated with the 3pecies of fungi stated in the table and incubated at about 21 deg.C.
Evaluation was carried 0l1t a~ker 4-10 day~, dependent upon the speed of growth of the fungi. When evaluation was carried out the radial growth of the mycelium on the t~eated nutrient media wa~ compared with the gr~w~h on the control nutrient medium. In the evaluation o~
the rungus growth~ the following characteri~tic values were used:
1 no ~ungus growth up to 3 very strong inhibition o~ growth Le A 18 038 - 31 -..

S

up to 5 medium inhibition of growth up to 7 ~light inhibition of growth 9 growth equal to that of untreated control.
The active compounds, th~ active compound concen t:ra~cions and the re~u~t~ can be seen ~rom the ~ollowing t ab le:

Le A 18 038 ~ 32 ~ f"~

-~= ~ ~

bO --1~ . .
r~ _ -- aB Z l~.I O
~ -.aau ~i~i~
~ snloqo~lq~~
----: umqo~
:~ ~ _o~a~lo~
~ ~ ~ o~
. ~ n,~
: ~ ~:
E~ '~:1 ~ o~
~ ~FUF~,'~ S
~3~ o~
Uml~I~ sn,~
.

o o .

P
." c~
t~ oo t,q o c~
,_ ~ ~ ~_ aô ^ '' ~rl ~ P:
c~
ec 1 Le ~ 1~ o38 - 33 ~

g~5 ;~.

CH2 - ~ - Cl 0 - CH ~ CH ~ C(CH3 )3 ~ M\ 5Q~ H
Nll x 1/2 ~ (1 Sû~H
A mixture o~ 900 ml o~ 33~ s~rength sodium hydroxide solution3 75 ml 4r a 50% ~rength solution of a butyl-dimethyldodecyl-ammonium ~3alt and 242 g (1.5 mol~ of ~,-chlorobenzyl chloride wa~ added dropwise to 222 g ( 0. 75 mol) o~ 1-(4 chlorophenoxy)-3,3-dimethyl-1-(1,2,4~tr~azol l-yl?-butan-2-ol in 700 ml of toluene. The mixture was stirred at 80C ~or 16 hours. After cooling, the or~anic phase was separated o~f, wa~hed with 2 litres o~ S~ stren~;th hydrochloric acid, dried over sodium sulpha~e and con~
centrated ~y distillin~ off the solvent in vacuo. ~hs oil which remained Wa8 taken up in 1.2 litres of acetone~
and a solukion o~ lQ0 g o~ 1,5-naphthalenedi~ulphonic acid in 500 ml Or acet one wa8 added. The crysk~lline precipitate was filtered of~g washed with 1,000 ml of a~eto~e and dried at 50C o~er phosphoru~ pentoxide in vacua. 280 g (6~g Or theory) of 2-(4-chlorobenzyl-oxy~-l (4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butane naphthalene-1,,5-disulphonate o~ melting point 1~0C were obtained.

~e A 18 038 - 34 7~i OH
Cl - ~ - O - CH - CH - C(CH3 )~
~N~

N~

587 g (2 mol3 of` 1-(4-chlorophenoxy) 3~3-dimethyl~
~l j2,4-triazol 1-yl)-butan-2-one were dis~olved in 3 litre of methanol. A total Or 80 g (2 mol) of ~odium boro-hydride was added, in portions of 5 g each, to this solutioll :
at O ~o 10Cs whilst stirring and cooling with ice, and ~hç
mlx~ure was stirred at 5 to 10C for 2 hour~ and then at room temperature for 12 hour~. It was then cooled to 10C
and 300 ~ ~ 3 mol) of concentrated aqueou~ hydrochloriç
acid were added at 10 to 20C. After stirring at room temperature for six hours, the re~ulting qu~pension was diluted with 3.8 litres of water which contained 400 g : t4.8 mol) of sodium bicarbonate. The precipitate thereby ~rmed wa3 filtered off. 502 g (85% ~ theory) of 1-(4-~h1Orophenoxy)-3,3-dimethyl-1-(1,2,l1-triazol-1-yl)-butan-2-ol o~ melting point 112-117C were obtained.

Cl - ~) - O - CH - CQ - C(CH3 )~

418 g ~6.6 mol) o~ 1~2,4-triazole were dissolved in 3,000 ml of acetone. 934 g (7.2 mol) of anhydrous, powdered potassium carbonate were added to this ~oluti~?
the suspension was heated to the boil and a solution o~

Le A 18 0~ ~ 35 ~

1,565 g ~6 mol~ o~ 1-(4-chlorophenoxy~ chloro-3~3-dime~hyl-butan-2-one in 1~500 ml of aCetone was added drop-wise in a manner ~uch that the mixture boiled under re~lux without heating. After the addition had ended, the ~ILix1;ure was heated under re~lux for 15 hours in order to bring th~
reaction to completion; the resulting precipitate was ther~
~iltered o~f " washed with acetone and di~carded. l~e ~iltrate was freed from ~olvent under a waterpump vacuum~
the residue was taken up in 3,000 ml o~ ~oluene and the ~oluene solution was wa~hed once with a aolution o:E 100 g of ~7% s~rength hydrochloric acid in 2,000 ml Or water.
rhe aqueous phase was separated o~f and discarded; the organic pha~e was washed with 5,000 ml o~ water and, a~ter adding further 4,000 ml o~ toluene, was stirred with a ~olution ~ 145 g of sodium hydroxide in 33500 mi of water at room temperature for 6 hours. Thereafter, the or~anic pha~e wa~ separated off, wa~hed with water until neutral and ~reed from sol~ent under a waterpump vacuum. 1,535 g (87g o~ theory) o~ 1 (4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-~0 triazol-1-yl)-butan-2-one of melting point 75-76C were obtained.
C~ 0 - CH - C~ - C(CH3 Cl 771 g (6 mol) o~ 4-chlorophenol were di~solved in 3~600 ml ~ acetone. 3 g of anhydrous ~odium iodide and 910 g (6.6 mol) o~ anhydrou~, powdered potassium carbonate we~e introduoed and 895 g (6.3 mol) o~ 94.6% pure mono-chloropinacoline were added drop~i~e under re~lux. A~ter ~ti~ring the mixture at the reflux temperature ~or 20 L~ A 18 038 - 36 -~lUq:~7~

hours, the precipitate was filtered off, washed with acetone and discarded. The filtrate was freed from solven1;
under a waterpump vacuum. The resulting white residue was taken up in 3,000 ml of carbon tetrachloride and the carbon tetrachloride solution was warmed to 60C. 831 g ~6.6 mol) of sulphuryl chloride were added dropwise to this solution3 without further warming, in a manner such that gas was continuously evolved. After the addition had ended3 the mixture was heated under reflux for 15 hours. Finally, the solvent was distilled o~f under a waterpump vacuum.
1,565 g of 1-(4-chlorophenoxy)-1-chloro-3,3-dimethyl-butan-2-one were obtained in quantitative yield and could be used in the reaction described above without further purification, ~

~ 0 - CH2 - CH = CH2 Br - ~ ~ 0 - CH - ~H - C(CH~ )3 ~ N ~ (2) N--34 g (0.1 mol) of 1-(4-bromophenoxy) 3,3-dimethyl-1-(1~2,4-triazol-1-yl)-butan-2-ol were suspended in 175 ml of dioxan and the suspension was added dropwise to a mixture of 3.5 g of 80% strength sodium hydride and 125 ml of dioxan, whilst stirring. ~hereafter~ the mixture was heated under reflux for one hour. After cooling, 14.5 g (C.12 mol) of allyl bromide were added dropwise at room temperature to the sodium salt thus obtained~ The mixture was then Le A 18 o~8 - 37 _ 11t)~;P975 heated under reflux for 15 hours~ allowed to cool and con-centrated by distilling off the solvent. The oily residue was taken up in 600 ml of methylene chloride and the methylene chloride solution was~washed twice with 1,000 ml Or water each time 3 dried over sodium sulphate and con-centrated. The residue was distilled under a high vacuum.
30 ~ ~79g of theory) of 2-allyloxy-1-(4-bromophenoxy)-3,3-dimethyl 1-(1,2,4-triazol-1-yl)-butane of boiling point 152-154C/0.2 mm Hg were obtained.
Example 3 Cl C~l2 - ~ - Cl Cl - ~ - 0 CH - CH - ~ - Cl N ~ N Cl N _ J

19.2 g (0.05 mol) of 1-(4~chlorophenoxy)-2-(2,4 -dichlorophenyl)-1-(1,2,4-triazol-1-yl)-ethan-2-ol were dissolved in 100 ml of dioxan and the solution was added dropwise to a mixture of 2 g o~ 80% strength sodium hydride in 100 ml o~ dioxan at 80C. A~ter the evolution of hydrogen had subsided, 10 g (0.05 mol) o~ 2,4-dichlorobenzyl chloride were added dropwise and ths mixture was heated under reflux for 15 hours. After coolingg the solvent was dis-tilled ofr in vacuo and the residue was taken up in 100 ml o~ water and 100 ml o~ methylene chloride. The organic phase was separated off, washed twice with 100 mi of water each time, dried over sodium sulphate and concentrated by Le A 18 038 - 38 -97~i distilling off the solvent in acuo~ The solid residue was recrystallised from ekher. 9 g C31% of theory) of 1-(4-chlorophenoxy)-2-(2,4-dichlorobenzyloxy) 2-(2,4~dichloro-phenyl)~ 2,4-triaæol-l-yl)-ethane of melting point 132-135C were obtained.
~ ..

Cl o - C2H~

Cl - ~ - 0 - 7H - CH - C(CH3 )3 N ~ (4) ~ N

33 g (0.1 mol) of 1-(2,4-dichlorophenoxy)-3,3-dimethyl-l-imidazol-l-yl-butan-2-ol were dissolved in 150 ml of dioxan and the solution was added dropwise to 3.5 g of 80% strength sodium hydride in 150 ml of dioxan. The mixture was stirrsd for 3 hours at room temperature. After addition of 13.1 g (0,12 mol) of ethyl bromide, the mixture was stirred under reflux for further 17 hours.

After cooling, the solvent was distilled off in vacuo, the residue was taken up in 600 ml of methylene chloride and the methylene chloride solution was washed twice with l,OC0 ml of water each time, dried over sodium sulphate and dis-tilled under a high vacuum. 10 g (28% of theory) of 2-ethoxy~ 2,4-dichlorophenoxy)-3,3-dimethyl-l-imidazol l-yl-butane of boiling point 170-175C/0.2 mm Hg were obtained.
The following compounds in Table 1 were obtained analo~ousl~.

Le A 18 038 - ~9 -o''~' _ ~ ~

I I K~ ~ ~ ~ S ~S

O--~ C~

~0 ~ ;t ~ ;t ;1~ J N
U ~ ~

u~ ~-1 Le A 18 038 - 40 -~,.

. ,~
0~ ~ 0 I~ 4 6 o bD~-- ~9 P: ~ ~ `.~ _ ~o ~ ~~i~ ~ r~ `~
.~ $ u~ p ,, ~ rl -~-' :

~ ~ ~ `J ~
: v ~ c~

¦ N ~ N ;1' 3 ~ ~ 3 ~ U

. I t.) ~ ~ 2; æ ~; æ ~ :z; z;

~, . ~ u~ o ~Z r~ 1 ~ ~ N
~1 Le A 18 038 - 41 -5~
o ~, X ~ o o o o ., o ~ ~ ~ o ~ 0 ~C~

:

~l . C~
~ P~ q q q q q c~ ~

~ y ~

¢ Z
c~ o ~æ
P~

Le A 18 038 ~ 42 -o~ ~ ~

~ o ~
D ~ ~ ~ ;~
d) &~ C~ ;l ~I t!` rl C~ O a~ o C"3 C,~~) V C~ V V ~ C~

m ~:

~ V ~ U

~
1 ~ ct~ o Le A 18 038 ~- 43 -~3 ~
O ~ ~.. ' E~ O

~ ~ ~ æ
O ~ ~ ¢ o ~_ ba~ ~ ~ o ~e OD~ ~ ~ m ~
ao o cr~

I~ V

. V ~ U V V C~
.

~ ~ N J ~ ~3 ~ 3 r~
r~: m n~ m . C~ ~ ~ V C~ C~
~ ~~ ~ ' V
Q~ ' ~æ ,, c~ 0 O~ O ,~

Le A 18 038 - 44 -g75 ~ ,_ o~ .~ ~ ~q -- ~: o o ~ ~ _~ ~
t r~ r 0 ~ ~ j~

~oS> t 3 0 a~
Ut t~ t~ ~ O
t~

V ~) : O
:: :
t~ O

f ~ J .
Ut ~ r 1 5N ~ C
I
; . 5 ~t a~ ~C Z; ~ '` ~
v .. '~ e ) ~ It ~1t~l 1~ 3 ~ 1 1 Z ~D ~ ~ Z; ~; ¢

Le A 18 0~8 - 45 ~ .
.

- , . . .. - .: . .. .. .

The following com~ounds of the general ~o~mula (I ) oould be prepared in a corre~ponding manner:
T a b` 1 e 2 A R X Y
.

CH CH~ 40Cl C~

CX C2 H5 4-Cl ~ ) Cl CH -CH2-CH=CH2 4-Cl ~Cl C

CH -CH2-C----CH 4-Cl ~)-Cl C

C~ Cl CH CH~ 2, 4~Cl2 ~-Cl C
CH C2 ~5 2, 4-C12 ~-Cl C
CH n-C H7 2, 4-Cl2 ~Cl C~ .

N -CH2 -C~ CH 4-Cl ~Cl C
N C2 ~s 2, 4-~12 ~)-Cl C
N n C~ H7 2, 4 -Cl2 ~-Cl C

Le A 18 038 - 46 -97~

A R Xn ........ Y

N GH3 4-F ~Cl N ~z ~ 4-F ~Cl N -CNz~Cl 4-F ~Cl Le A18 038 - 47 -. . .. -.,. -i...... . ~ . . ~

Claims (18)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An azolyl ether derivative of the formula (I) in which A is CH or a nitrogen atom, R is alkyl; alkenyl; alkynyl; benzyl; benzyl substituted with a sub-stituent selected from halogen, cyano, nitro, alkyl, alkoxycarbonyl, and halo-genoalkyl; phenyl; or phenyl substituted by nitro, cyano or alkoxycarbonyl, and optionally additionally substituted by a substituent selected from halogen, alkyl and halogenoalkyl;
X is halogen; alkyl; alkoxy; alkylthio; alkylsulphonyl; halogeno-alkyl; alkoxycarbonyl; nitro; cyano; phenyl; phenoxy, phenylthio; or phenyl, phenoxy or phenylthio substituted by a substituent selected from halogen, cyano, nitro and halogenoalkyl;
n is o, 1, 2, 3, 4 or 5;
Y is alkyl; alkyl substituted with a substituent selected from halo-gen, hydroxyl, cyano, and the grouping -CO-OR1; -CO-NR2R3 or -O-CO-R4; phenyl;
or phenyl substituted by halogen;
R1 is alkyl;
. R2 and R3 each independently is hydrogen; allkyl; phenyl or phenyl substituted by halogen; and R4 is alkyl; halogenoalkyl; phenyl; benzyl; phenyl or benzyl substi-tuted by halogen; or cycloalkyl, or a non-phytotoxic salt or metal complex thereof.

2. A compound according to claim 1, in which R is alkyl, alkenyl or alkynyl each with up to 4 carbon atoms;

benzyl; benzyl substituted with a substituent selected from halogen, cyano, nitro, alkyl with 1 to 4 carbon atoms, alkoxycarbonyl with 1 to 4 carbon atoms in the alkyl part and halogenoalkyl with up to 2 carbon atoms and up to three halogen atoms; phenyl; phenyl substituted by nitro, cyano or alkoxycarbonyl with 1 to 4 carbon atoms in the alkyl part, and optionally additionally substi-tuted by a substituent selected from halogen, alkyl with 1 to 4 carbon atoms and halogenoalkyl with up to 2 carbon atoms and up to three halogen atoms;
X is halogen; nitro; cyano; C1-C4 alkyl, C1-C4 alkoxy; C1-C4 alkyl thio; C1-C4 alkylsulphonyl; alkoxycarbonyl with 1 to 4 carbon atoms in the alkyl part; halogenoalkyl with up to 4 carbon atoms and up to 5 halogen atoms; phenyl; phenoxy; phenylthio; or phenyl, phenoxy or phenylthio substi-tuted by a substituent selected from halogen, cyano, nitro and halogenoalkyl with up to 2 carbon atoms and up to 3 identical or different halogen atoms;
n is 0, 1, 2 or 3; and Y is alkyl with 1 to g carbon atoms; alkyl with 1 to 9 carbon atoms substituted with a substituent selected from halogen, hydroxyl, cyano, and the grouping -CO-OR1; -CO-NR2R3 or -O-CO-R4; phenyl; or phenyl substituted by halogen;
R1 is alkyl with 1 to 4 carbon atoms;
R2 and R3 each independently is hydrogen; alkyl with 1 to 4 carbon atoms;
phenyl; or phenyl substituted by halogen;
R4 is alkyl with 1 to 18 carbon atoms; halogenoalkyl with 1 to 4 carbon atoms and 1 to 3 halogen atoms; phenyl; benzyl; phenyl or benzyl substituted by halogen; or cycloalkyl with 5 or 6 carbon atoms.

3. A compound according to claim 1, wherein such compound is 1-(4-chlorophenoxy)-2-methoxy-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butane of the formula

4. A compound according to claim 1, wherein such compound is 1-(4-biphenylyloxy)-2-ethoxy-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butane of the formula

5. A compound according to claim 1, wherein such compound is 1-(4-chlorophenoxy)-2-ethoxy-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butane of the formula

6. A compound according to claim 1, wherein such compound is 1-(4 bromophenoxy)-2-(2,4-dichlorobenzyloxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butane of the formula

7. A compound according to claim 1, wherein such compound is 1-(4-biphenylyloxy)-2-methoxy-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butane of the formula

8. A method of combatting fungi which comprises applying to the fungi or to a habitat thereof, a fungicidally effective amount of a compound accord-ing to claim 1.

9. A method according to claim 8, wherein the compound is applied in the form of a composition comprising said compound as active ingredient in admixture with a suitable diluent or carrier.

10. A method according to claim 9, wherein the composition comprises 0.00001 to 0.1% by weight of said active ingredient.

11. A method according to claim 9, wherein the composition comprises 0.0001 to 0.05% by weight of said active ingredient.

12. A method according to claim 8 wherein the active ingredient is applied to soil in an amount of 1 to 1000 g per cubic metre of soil.

13. A method according to claim 8 wherein the active ingredient is applied to soil in an amount of 10 to 200 g per cubic metre of soil.

14. A method according to claim 8 in which the active compound is applied to seed in an amount of 0.001 to 50 g per kg of seed.

15. A method according to claim 8 in which the active compound is applied to seed in an amount of 0.01 to 10 g per kg of seed.

16. A method according to claim 8 or 10, wherein the active ingredient is a compound as defined according to claim 2.

17. A method for combatting fungi which comprises applying to the fungi or to a habitat thereof, a fungicidally effective amount of a compound accord-ing to claim 3, 4 or 5.

18. A method for combatting fungi which comprises applying to the fungi or to a habitat thereof, a fungicidally effective amount of a compound accord-ing to claim 6 or 7.